Saponification value

Saponification value is a measure of the content of ester linkages. It is determined by back titration of potassium oxide in the presence of phenolphthalein indicator with 0.5 N sulfuric or hydrochloric acid. First, a sample is mixed with 25 ml of alcohohc solution of KOH and left for 1 h in a steam bath to react. The amount of the sample is selected in such a way that about a half of KOH (45 to 55%) is used in the reaction. 

ISO standard specifies the amount of phthalate sample which is to be taken for analysis relative to its molecular weight. 50 ml of IN alcoholic KOH and 5 ml of water are added to the sample which is then refluxed for 1 h. Phenolphthalein soluhon is then added and the sample is htrated with 1 N HCl. 

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Fat or oil Solidification point, °C Specific gravity (15°C/15°C) Refractive index Acid value Saponification value Iodine value... 

Refractive index Acid value Saponification value Iodine value... 

Free Fatty Acid and Saponification Value. High concentrations of free fatty acid are undesirable in cmde triglyceride oils because they... 

Hydrolysis. The first effect of either acid hydrolysis or alkaline hydrolysis (saponification) is the removal of the fatty acids. The saponification value of commercial lecithin is 196. Further decomposition into glycerol, phosphoric acid, and head groups (ie, choline, ethanolamine, etc) may foUow prolonged heating. Lecithin may also be hydrolyzed by enzymes. 

Trinidad asphalt has a relatively uniform composition of 29% water and gas, 39% bitumen soluble in carbon disulfide, 27% mineral matter on ignition, and 5% bitumen that remains adsorbed on the mineral matter. Refining is essentially a process of dehydration by heating the cmde asphalt to ca 165°C. The refined product averages 36% mineral ash with a penetration at 25°C of about 2 (0.2 mm), a softening point (ring and ball method) of 99°C, a flash point (Cleveland open cup) of 254°C, a sulfur content of 3.3%, and a saponification value of 45 mg KOH/g. The mineral matter typically contains... 

The American Society for Testing and Materials (ASTM) and the American Oil Chemists Society (AOCS) provide standard methods for determining properties that are important in characterization of dimer acids. Characterization of dimer acids for acid and saponification values, unsaponiftables, and specific gravity are done by AOCS standard methods ... 

It is soluble in about 5 volumes of 70 per cent, alcohol. This ester has the character of being saponified much more slowly than most other esters, so that in any determination in which it is involved it is necessary to saponify the sample for two hours before it is safe to consider the reaction complete. This fact also assists in determining whether terpinyl acetate is present as an adulterant in natural essential oils, for if the saponification value as determined by thirty minutes saponification is materially lower than that as determined by a two hours saponification, it may be fairly safely inferred that terpinyl acetate or some similar ester is present. 

Strictly speaking the amount of free acids present in an essential oil should be determined, and the acid value deducted from the saponification value, the difference being the ester value. 

The high saponification value of these two bodies render them particularly suitable for adulteration, a small proportion being sufficient to materially raise the ester value. 

Terpinyl acetate in the absence of esters of high molecular weight, or ethyl esters of the fatty acids of coconut oil, is indicated by a difference to be observed in the apparent ester value by different times of saponification. This ester is far more resistant to the action of caustic alkali than is linalyl acetate, and requires two hours at least for complete saponification. Hence, if the oil shows a difference in the saponification value in thirty minutes and in two hours, which amounts to more than from 1 to 2, terpinyl acetate is almost certainly present. The following table shows the effect of this partial-saponrfication on the two esters and on adulterated oils —... 

The author has recommended the examination of the last 10 per cent, left on evaporation of the oil on a water-bath, since the heavy artificial esters accumulate in this fraction. The refractive index of this 10 per cent, should not be below 1 5090, and the saponification value should not exceed 190. The following figures (see p. 317) represent nine samples of adulterated oil, all sold as genuine bergamot oil. 

Schimmel Co. have proposed to detect esters of fixed acids by an estimation of the amount of volatile acids obtained by distilling the acidified saponification residues, and comparing this figure with the amount of acid indicated by the saponification value. 

B = Saponification value of the original oil after acetylation (not of saponified oil). 

The Oximation process depends on the fact that citronellal oxime, produced by shaking in the cold with a solution of hydroxylamine, is converted on heating with acetic anhydride into a nitrile which is not affected by saponification with alcoholic potash. The difference between the molecular weight of the nitrile formed and that of citronellal is so small as to be negligible, and the calculation of the percentage of geraniol from the saponification value is made by the usual formula. The method of procedure is as follows —... 

Discussion. For oils and fats, which are esters of long-chain fatty acids, the saponification value (or number) is defined as the number of milligrams of potassium hydroxide which will neutralise the free fatty acids obtained from the hydrolysis of 1 g of the oil or fat. This means that the saponification number is inversely proportional to the relative molecular masses of the fatty acids obtained from the esters. A typical reaction from the hydrolysis of a glyceride is ... 

F-test 140, (T) 841 Faraday constant 60, 504 Faraday s laws 503, 504 Fast sulphon black F 319 Fats D. of saponification value, (ti) 308 Ferric alum indicator see Ammonium iron(III) sulphate... 

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